Mordant azo-dyestuffs



Patented May 8, 195T UNITED STATES PATENT OFFICE MORDAN T AZO-DYESTUFFS Max Miiller, Basel, and Jiirg Ostertag, Riehen, near Basel, Switzerland, assignors to Durand & Huguenin A. G., Basel, Switzerland, aSwiss N Dr wing- Application December 1% 199,51:-

rial No, 132,988. In Switzerland December 15,

4 Claims.

According to this invention, valuable new mordant azo dyestuffs are made by condensing a nitro-monoazo dyestuff which corresponds to the formula HOOC I X Y wherein X represents hydrogen or a lower alkyl radical and Y represents hydrogen or SOsH, in an alkaline medium with an amino-aryl ketone which corresponds to the formula coon HrN

wherein R1 stands for hydrogen, SQaI-I or halo- 20 gen, and R2 stands for hydrogen or SQsH.

HOOC

The amino-diaryl ketones may be obtained, for example, by the Friedel-Craits reaction by condensing a nitro-substituted carboxylic acid halide with'an alkyl ester of an aromatic ortho-hydroxy-carboxylic acid, hydrolysing the resulting ester, and reducing the nitro-group in the product to a free amino group (compare Limprich, Annalen der Chemie, vol. 290, page 170).

The new dyestuffs obtainable by the above process correspond to the formula and are especially suitable for chrome printing on 45 cellulose fibres, whereby there are produced principally orange to brown prints which are distinguished by excellent properties of wet frastness and also fastness to chlorine and light. The new dyestuffs are also suitable for dyeing protective 50 dissolves in water with. an orange colouration and 2 oxide coatings on aluminium and-its alloys, whereby there are produced principally golden tints having excellent properties of fastness.

The following examples illustrate the-inverte- 5 tion, the parts being by weight:

Example 1 36.7 parts of 4-nitro-4-hydroxy-3'-carboxy- 1:1'-azobenzene-3-sulphonic acid and 25.? parts of 1-(4'-amin0 benzoyl) 4 hydroxybenzene 3-carboxylic acid are heated with 400 parts of caustic soda solution of about 8 per cent strength for hours at the boilv under reflux. The excess 15 of alkali is then neutralised with hydrochloric acid until the reaction is feebly alkaline, the whole is allowed to c001 and the precipitated condensation productisisolat d- The new azodyestuff which corresponds to the formula COOH in concentrated sulphuric acid with a reddishblue colouration. In chrome printing on cotton it yields strong orange prints which are distinguished by excellent-properties of wet iastness, and also fastness to chlorine and light.

A dyestufi having similar properties is ob- ,tained by using, insteadof 1-(4'-aminobenzoyl)- 4 hydroxybenzene} 3 carboxylic acid, 1 e (4 aminobenzoyl) 4 hydroxybenzene 3 car- COOH boxylic acid--sulphonic acid. The dyestuff so. obtained dyes, ior- -'.exa p e, anodically oxidised aluminium golden tintsh-aving very good properties of iastness.

Example 2 36.7 parts. or tnitrc-11ydroxy#3carboxy- The ne w azo dyestuff which corresponds to the formula N 11000 so,H

dissolves in water with an orange colouration and in concentrated sulphuric acid with a blue-violet colouration. In chrome printing on .cotton it yields orange-brown prints which are distinguished by excellent properties of wet fastness, and also fastness to chlorine and light.

Dyestufis having similar properties are obtained by using instead bf 1-(4-aminobenzoyl) 4-hydroxybenzene-3-carboxylic acid--su1phonic acid, l (4 -aminobenzoyl-3 -sulphonic acid) -4- hydroxybenzene-3-carboxylic acid or 1-(4'-aminobenzoyl-B -sulphonic acid) -4hydroxybenzene- 3-carboxylic acid-5-sulphonic acid.

dissolves in water with an orange colouration and Example 3 36.? parts of 3-nitro-4'hydroxy-3'-carboxy- 1z1 -azobenzene-4-sulphonic acid and 25.7 parts of 1-(4-aminobenzoyl) 4 hydroxybenzene 3 carboxylic acid are heated with 400 parts of caustic soda solution of about 8 per cent strength for 20-24 hours at the boil under reflux. The excess of alkali is then neutralised with hydrochloric acid until the reaction is feebly alkaline, the whole is allowed to cool, and the precipitated condensation product is isolated.

The new dyestufi dissolves in water with an orange colouration and in concentrated sulphuric acid with a yellowish-brown colouration. In chrome printing on cotton the dyestuff yields yellowish orange-brown prints which are in part distinguished by excellent properties of wet fastness, and also fastness to chlorine and light.

By using 3-nitro-4-hydroxy-3'-carboxy-1:1- azobenzene-(i-sulphonic acid, instead of 3-nitro- 4 hydroxy 3 carboxy 1:1 azobenzene 4-sulphonic acid, there is obtained a dyestulT having similar properties.

Example 4 38.1 parts of 4-nitro-5-methyl-4'-hydroxy-3- carboxy-l:1'-azobenzene-2-sulphonic acid and 25.7 parts of l-(4'-aminobenzoyl) -4-hydroxybenzene-B-carboxylic acid are heated with 400 parts of caustic soda solution of about 6 per cent strength for 10 hours at the boil under reflux. The excess of alkali is neutralised with hydrochloric acid until the reaction is feebly alkaline,

the whole is allowed to cool and the precipitated condensation product is isolated. p

The new dyestufi dissolves in water with a red- .4 orange colouration and in concentrated sulphuric acid with a blue colouration. In chrome printing on cotton it yields strong red-brown prints, which are distinguished by excellent properties of wet fastness, and also fastness to chlorine and light.

By using 4-nitro-6'-methyl-4'-hydroxy-3'- carboxy-l:1'-azobenzene-2-sulphonic acid, instead of 4-nitro-5'-methyl-4-hydroxy-3-carboxy-1:1'-azobenzene-2-sulphonic acid, a dyestufl having similar properties is obtained.

OOOH

Example 5 SO H COOH in concentrated sulphuric acid with a violet colouration. In chrome printing on cotton it yields strong orange-brown prints which are distinguished by excellent properties of wet fastness and fastness to chlorine and light.

Dyestuffs having similar properties are obtained by using instead of l-(3-arninobenzoyl)- 4-hydroxybenzene3-carboxylic acid, l-(3-aminobenzoyl) -4-hydroxybenZene-3 carboxylic acid- S-sulphonic acid, or l-(3-an1inobenzoyl-4-sulphonic acid) 4 hydroxybenzene 3 carboxylic acid, or l-(4-chloro-3-aminobenzoyl)-4-hydroxybenzene3carboxylic acid.

Example 6 30.9 parts of 4-nitro-4'-hydroxy-3-carboxy- 1:1-azobenzene in the form of the sodium salt and 33.7 parts of l-(-aminobenzoyl)-4.-hy droxybenzene-3-carboxylic acid-5-sulphonic acid are heated with 600 parts of caustic soda solution of about 8 per cent strength for 20 hours at the boil under reflux. After cooling, the excess of alkali is neutralised with hydrochloric acid until the reaction is feebly alkaline and the precipitated condensation product is isolated.

The new dyestuff dissolves in water with an orange colouration and in concentrated sulphuric acid With'a blue-violet colouration. In chrome printing on cotton it yields orange prints which in part have very good properties of wet fastness and also fastness to chlorine and light.

By using, instead of 4-nitro-4-hydroXy-3'- carboxy-l U-azobenzene, 4-nitro5'-methyl-4'- hydroxy-3-carboxy-l:1-azobenzene or l-nitro- 4'-hydroxy-3-carboxy-5'-sulphonic acid 1:1'-

, azobenzene there are obtained dyestufis having similar properties.

5 We claim: 1. The azo dyestufis of the general formula 6 fibres in the chrome-printing process orange shades.

COOH

wherein X means a member selected from the HOOC group consisting of hydrogen and lower alkyl radicals, Y means a member selected from the group consisting of hydrogen and SOsI-I, R1 means a member selected from the group consisting of hydrogen, SO3H and halogen and R2 means a HOOC member selected from the group consisting of hydrogen and SOsH, being orange to brown powders, dissolving in water with orange to brown colouration and dyeing cellulosic fibres in the chrome-printing process orange to brown shades.

2. The azo dyestufi of the formula HOOC 50311 30 being a red-brown powder, dissolving in water 3. The azo dyestuff of the formula 503E (I30 OH SOaH being a red-brown powder, dissolving in water with an orange colouration and dyein oellulosic 20 fibres in the chrome-printing process orangebrown shades.

4. The azo dyestufi of the formula COOH with an orange colouration and dyeing cellulosic fibres in the chrome-printing process orange- 35 brown shades.

COOH

being a red-brown powder, dissolving in water with an orange colouration and dyeing cellulosic M:QX MiiLLER. JORG" OSTERTAG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 406,670 Sandmeyer -d July 9, 1889 613,911 Ris Nov. 8, 1898 1,552,058 Kalischer et a1. Sept. 1, 1925 Keller Apr. 5, 1949 

1. THE AZO DYESTUFF OF THE GENERAL FORMULA 